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JP6195419B2 - Radical polymerizable group-containing silicone compound and method for producing the same - Google Patents

Radical polymerizable group-containing silicone compound and method for producing the same Download PDF

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JP6195419B2
JP6195419B2 JP2014212682A JP2014212682A JP6195419B2 JP 6195419 B2 JP6195419 B2 JP 6195419B2 JP 2014212682 A JP2014212682 A JP 2014212682A JP 2014212682 A JP2014212682 A JP 2014212682A JP 6195419 B2 JP6195419 B2 JP 6195419B2
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智幸 後藤
智幸 後藤
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Shin Etsu Chemical Co Ltd
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Description

本発明は末端にラジカル重合性基を有するシリコーン化合物及びその製造方法に関する。詳細には、酸素透過性に優れ、室温での取り扱い性が良好であるシリコーン化合物及びその製造方法に関する。   The present invention relates to a silicone compound having a radical polymerizable group at a terminal and a method for producing the same. In detail, it is related with the silicone compound which is excellent in oxygen permeability, and the handleability at room temperature is favorable, and its manufacturing method.

従来、コンタクトレンズ材料のためのシリコーンハイドロゲルが開発されており、酸素透過性を向上させるため、あるいはレンズの柔軟性付与及び機械的強度の向上目的で、重合性基を有するシリコーン化合物（ポリジメチルシロキサン）が原材料として採用されている（非特許文献１）。例えば、米国特許第３８０８１７８号（特許文献１）には、眼科デバイスに用いられるシリコーンモノマーとして、３−［トリス（トリメチルシロキシ）シリル］プロピルメタクリレート（ＴＲＩＳ）が記載されている。シリコーンハイドロゲルは、親水性モノマーと重合性のシリコーン化合物を共重合させて得るため、親水性モノマーとの相溶性が重要である。しかしＴＲＩＳは親水性モノマーとの相溶性に劣る。親水性モノマーとの相溶性を高めるためにシリコーン化合物中にアミド基、ウレタン基、あるいはヒドロキシル基などの極性官能基を導入する方法が知られている（非特許文献１、特許文献２及び３）。   In the past, silicone hydrogels for contact lens materials have been developed. Silicone compounds having a polymerizable group (polydimethyl) are used to improve oxygen permeability or to provide flexibility and mechanical strength of the lens. Siloxane) is employed as a raw material (Non-patent Document 1). For example, US Pat. No. 3,808,178 (Patent Document 1) describes 3- [tris (trimethylsiloxy) silyl] propyl methacrylate (TRIS) as a silicone monomer used in ophthalmic devices. Since the silicone hydrogel is obtained by copolymerizing a hydrophilic monomer and a polymerizable silicone compound, compatibility with the hydrophilic monomer is important. However, TRIS is inferior in compatibility with hydrophilic monomers. In order to enhance the compatibility with the hydrophilic monomer, a method of introducing a polar functional group such as an amide group, a urethane group, or a hydroxyl group into the silicone compound is known (Non-patent Document 1, Patent Documents 2 and 3). .

特許文献４には、３−［トリス（トリメチルシロキシ）シリル］プロピルアクリルアミド（ＴＲＩＳ−Ａ）をモノマー成分として含む眼用レンズ製造用組成物が記載されている。ＴＲＩＳ−Ａは、ラジカル重合性基としてアクリル基を有するためＵＶ硬化性に優れ、コンタクトレンズ原材料の一つとしてよく用いられている。しかしＴＲＩＳ−Ａは室温で固体（融点：約５０℃）であり、取り扱い性が悪いという問題があった。   Patent Document 4 describes a composition for producing an ophthalmic lens containing 3- [tris (trimethylsiloxy) silyl] propylacrylamide (TRIS-A) as a monomer component. Since TRIS-A has an acrylic group as a radical polymerizable group, it has excellent UV curability and is often used as one of contact lens raw materials. However, TRIS-A is a solid (melting point: about 50 ° C.) at room temperature, which has a problem of poor handling.

米国特許第３８０８１７８号U.S. Pat. No. 3,808,178 特開２００７−１８６７０９号公報JP 2007-186709 A 特表２００７−５２６３６４号公報Special table 2007-526364 国際公開公報第２０１２／１３０９５６号International Publication No. 2012/130956

先端バイオマテリアルハンドブック、秋吉一成、石原一彦、山岡哲二監修、第５章５節Ｐ．５２８−５３３、「コンタクトレンズ材料」Advanced Biomaterials Handbook, Kazunari Akiyoshi, Kazuhiko Ishihara, Tetsuji Yamaoka, Chapter 5 Section 5 528-533, "Contact Lens Material"

そのため本発明は、優れた酸素透過性を有する硬化物を与え、室温で液体であり取り扱い性が良く、さらに反応性が良好である、ラジカル重合性基含有シリコーン化合物を提供することを目的とする。   Therefore, an object of the present invention is to provide a radically polymerizable group-containing silicone compound that gives a cured product having excellent oxygen permeability, is liquid at room temperature, has good handleability, and has good reactivity. .

本発明者らは、上記課題を解決すべく鋭意検討を重ねた結果、下記式（６）で示されるシリコーン化合物を見出した。即ち本発明は、下記式（６）で表される、シリコーン化合物

Figure 0006195419
（式中、Ｒ １ は水素原子またはメチル基であり、Ｒ ２ 及びＲ ４ は互いに独立に、炭素数１〜１０のアルキル基であり、ｎは１〜６の整数であり、ｍは１〜６の整数であり、ｅは互いに独立に１、２、又は３である）
及び該シリコーン化合物の製造方法を提供する。 As a result of intensive studies to solve the above problems, the present inventors have found a silicone compound represented by the following formula ( 6 ). That is, the present invention provides a silicone compound represented by the following formula ( 6 ):
Figure 0006195419
 Wherein R 1 is a hydrogen atom or a methyl group, R 2 and R 4 are each independently an alkyl group having 1 to 10 carbon atoms, n is an integer of 1 to 6, and m is 1 to 6 is an integer, and e is 1, 2, or 3 independently of each other)
And a method for producing the silicone compound.

本発明のシリコーン化合物は、室温で液体であることができ、取り扱い性が良く、且つ、酸素透過性に優れた硬化物を与える。さらに反応性が良好である。   The silicone compound of the present invention can be a liquid at room temperature, provides a cured product with good handleability and excellent oxygen permeability. Furthermore, the reactivity is good.

以下、本発明について、詳細に説明する。   Hereinafter, the present invention will be described in detail.

本発明は下記式（１）で表されるシリコーン化合物である。

Figure 0006195419
（式（１）中、Ａは互いに独立に、置換又は非置換の、炭素数１〜６の、分岐構造を有しても良い二価炭化水素基であり、Ｂは互いに独立に、ケイ素原子数２〜２０個を有するオルガノシリコーンからなる一価の基であり、Ｘはラジカル重合性基を有する一価の基である）
該シリコーン化合物は、ラジカル重合性基（Ｘ）とシロキサン鎖（Ｂ）が窒素原子を介して結合しており、該窒素原子上にシロキサン鎖が二つ結合していることを特徴とする。当該構造により良好な酸素透過性を有することができる。また、本発明の化合物は室温で液体であることができ取り扱い性が良い。これはラジカル重合性基（Ｘ）とシロキサン鎖（Ｂ）を結合する窒素原子上に水素原子を有さないためである。 The present invention is a silicone compound represented by the following formula (1).
Figure 0006195419
 (In Formula (1), A is a substituted or unsubstituted divalent hydrocarbon group having 1 to 6 carbon atoms, which may have a branched structure, and B is independently of each other a silicon atom. A monovalent group composed of an organosilicone having a number of 2 to 20, and X is a monovalent group having a radical polymerizable group)
The silicone compound is characterized in that the radical polymerizable group (X) and the siloxane chain (B) are bonded via a nitrogen atom, and two siloxane chains are bonded on the nitrogen atom. The structure can have good oxygen permeability. In addition, the compound of the present invention can be liquid at room temperature and is easy to handle. This is because there is no hydrogen atom on the nitrogen atom that bonds the radical polymerizable group (X) and the siloxane chain (B).

上記式中、Ａは互いに独立に、置換又は非置換の、炭素数１〜６の分岐構造を有しても良い二価炭化水素基である。該二価炭化水素基としては、エチレン、１，３−プロピレン、１−メチルプロピレン、１，１−ジメチルプロピレン、２−メチルプロピレン、１，２−ジメチルプロピレン、１，１，２−トリメチルプロピレン、１，４−ブチレン、２−メチル−１，４−ブチレン、２、２−ジメチル−１，４−ブチレン、３−メチル−１，４−ブチレン、２，３−ジメチル−１，４−ブチレン、２，２，３−トリメチル−１，４−ブチレン、１，５−ペンチレン、１，６−ヘキサニレンが挙げられる。これらの基の炭素原子に結合した水素原子の一部または全部が、塩素、フッ素等のハロゲン原子で置換されたハロゲン化アルキレン基等であってもよい。好ましくは炭素数２〜５の直鎖構造の二価炭化水素基である。   In the above formula, A is a divalent hydrocarbon group which may be substituted or unsubstituted and may have a branched structure having 1 to 6 carbon atoms. Examples of the divalent hydrocarbon group include ethylene, 1,3-propylene, 1-methylpropylene, 1,1-dimethylpropylene, 2-methylpropylene, 1,2-dimethylpropylene, 1,1,2-trimethylpropylene, 1,4-butylene, 2-methyl-1,4-butylene, 2,2-dimethyl-1,4-butylene, 3-methyl-1,4-butylene, 2,3-dimethyl-1,4-butylene, Examples include 2,2,3-trimethyl-1,4-butylene, 1,5-pentylene, and 1,6-hexanylene. A halogenated alkylene group in which some or all of the hydrogen atoms bonded to the carbon atoms of these groups are substituted with a halogen atom such as chlorine or fluorine may be used. A divalent hydrocarbon group having a straight chain structure having 2 to 5 carbon atoms is preferred.

上記式中、Ｘはラジカル重合性基を含有する一価の基である。ラジカル重合性基としては、(メタ)アクリル基、スチリル基、インデニル基、アルケニル基、シクロアルケニル基、ノルボニル基、及び共役又は非共役アルカジエン基等が挙げられる。該Ｘは、例えば、下記（３）または（４）で示される基が好ましい。

Figure 0006195419
上記式（３）及び（４）において、Ｒ１は水素原子またはメチル基である。好ましくは反応性の観点からＲ１は水素原子であるのがよい。 In the above formula, X is a monovalent group containing a radical polymerizable group. Examples of the radical polymerizable group include (meth) acryl group, styryl group, indenyl group, alkenyl group, cycloalkenyl group, norbornyl group, and conjugated or non-conjugated alkadiene group. X is preferably a group represented by the following (3) or (4), for example.
Figure 0006195419
 In the above formulas (3) and (4), R 1 is a hydrogen atom or a methyl group. Preferably, R 1 is a hydrogen atom from the viewpoint of reactivity.

上記式中、Ｂは互いに独立に、ケイ素原子数２〜２０個、好ましくはケイ素原子数２〜１０個を有するオルガノシリコーンからなる一価の基である。該シリコーンの構造としては、直鎖状、分岐状または環状のものが挙げられる。該Ｂとして例えば下記（２）で表されるオルガノシロキサン構造が挙げられる。

Figure 0006195419
式中、Ｒ２、Ｒ３、及びＲ４は互いに独立に、炭素数１〜１０のアルキル基、または、炭素数６〜１２のアリール基であり、ｂは１〜３の整数であり、ｃは１〜３の整数であり、ｄは０〜３の整数であり、ｇは０〜１０の整数であり、ｈは０〜２の整数であり、ａは０〜３の整数であり、但しａ、ｈ及びｇは全てが同時に０ではない。 In the above formula, B is independently a monovalent group composed of an organosilicone having 2 to 20 silicon atoms, preferably 2 to 10 silicon atoms. Examples of the structure of the silicone include linear, branched or cyclic structures. Examples of B include an organosiloxane structure represented by the following (2).
Figure 0006195419
 In the formula, R 2 , R 3 , and R 4 are each independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, b is an integer of 1 to 3, and c Is an integer from 1 to 3, d is an integer from 0 to 3, g is an integer from 0 to 10, h is an integer from 0 to 2, and a is an integer from 0 to 3, provided that a, h and g are not all 0 at the same time.

中でもｇ＝０であり、ｈ＝０である、下記式で示される短鎖の分岐構造が好ましい。

Figure 0006195419
（ａは２または３であり、特に好ましくは３である。ｂは１〜３の整数であり、好ましくは１〜２の整数であり、特に好ましくは１である。Ｒ２及びＲ４は上記の通りである。） Among them, a short-chain branched structure represented by the following formula where g = 0 and h = 0 is preferable.
Figure 0006195419
 (A is 2 or 3, particularly preferably 3. b is an integer of 1 to 3, preferably an integer of 1 to 2, particularly preferably 1. R 2 and R 4 are the same as above. It is as follows.)

特に好ましくは、他のモノマーとの溶解性の観点から、下記で表されるシリコーン構造であるのがよい。

Figure 0006195419
Particularly preferred is a silicone structure represented by the following from the viewpoint of solubility with other monomers.
Figure 0006195419

上記式（１）で表されるシリコーン化合物は、好ましくは下記式（５）または（６）で表される。

Figure 0006195419
（式中、Ｒ１は水素原子またはメチル基であり、特に好ましくは水素原子である。Ｒ２及びＲ４は互いに独立に、炭素数１〜１０のアルキル基であり、ｎは１〜６の整数であり、ｍは１〜６の整数であり、ｅは互いに独立に１、２または３であり、好ましくは、ｅは２又は３であり、特に好ましくは、ｅは３である）
Figure 0006195419
 （式中、Ｒ１は水素原子またはメチル基であり、特に好ましくは水素原子である。Ｒ２及びＲ４は互いに独立に、炭素数１〜１０のアルキル基であり、ｎは１〜６の整数であり、ｍは１〜６の整数であり、ｅは互いに独立に１、２または３であり、好ましくは、ｅは２又は３であり、特に好ましくは、ｅは３である） The silicone compound represented by the above formula (1) is preferably represented by the following formula (5) or (6).
Figure 0006195419
 (Wherein R 1 is a hydrogen atom or a methyl group, particularly preferably a hydrogen atom. R 2 and R 4 are each independently an alkyl group having 1 to 10 carbon atoms, and n is 1 to 6) M is an integer of 1 to 6, e is 1, 2 or 3 independently of each other, preferably e is 2 or 3, particularly preferably e is 3.
Figure 0006195419
 (Wherein R 1 is a hydrogen atom or a methyl group, particularly preferably a hydrogen atom. R 2 and R 4 are each independently an alkyl group having 1 to 10 carbon atoms, and n is 1 to 6) M is an integer of 1 to 6, e is 1, 2 or 3 independently of each other, preferably e is 2 or 3, particularly preferably e is 3.

特に好ましくは、下記式（５’）または（６’）で表されるシリコーン化合物である。

Figure 0006195419
（式中、Ｒ１は水素原子またはメチル基であり、特に好ましくは水素原子である。Ｒ４はメチル基であり、ｎは１〜６の整数であり、好ましくは、ｎは３である。ｅは１、２または３であり、好ましくは、ｅは２又は３であり、特に好ましくは、ｅは３である）
Figure 0006195419
 （式中、Ｒ１は水素原子またはメチル基であり、特に好ましくは水素原子である。Ｒ４はメチル基であり、ｎは１〜６の整数であり、好ましくは、ｎは３である。ｅは１、２または３であり、好ましくは、ｅは２又は３であり、特に好ましくは、ｅは３である） Particularly preferred is a silicone compound represented by the following formula (5 ′) or (6 ′).
Figure 0006195419
 (In the formula, R 1 is a hydrogen atom or a methyl group, particularly preferably a hydrogen atom. R 4 is a methyl group, n is an integer of 1 to 6, and preferably n is 3. e is 1, 2 or 3, preferably e is 2 or 3, particularly preferably e is 3.
Figure 0006195419
 (In the formula, R 1 is a hydrogen atom or a methyl group, particularly preferably a hydrogen atom. R 4 is a methyl group, n is an integer of 1 to 6, and preferably n is 3. e is 1, 2 or 3, preferably e is 2 or 3, particularly preferably e is 3.

特に上記式において、Ｒ１が水素原子であるアクリル基含有シリコーン化合物は硬化性（反応性）に優れるため好ましい。 In particular, in the above formula, an acrylic group-containing silicone compound in which R 1 is a hydrogen atom is preferable because of excellent curability (reactivity).

本発明はさらに上記式（１）で表されるシリコーン化合物の製造方法を提供する。該製造方法は、下記式（８）で表される化合物と

Figure 0006195419
（式（８）中、Ｙはラジカル重合性基を有する一価の基であり、Ｚはアミンと反応する基またはハロゲン原子である）
下記式（９）で表される化合物
Figure 0006195419
 （式中、Ａ及びＢは上記の通りである）
とを反応させる工程を含む。前記工程を経ることにより室温で液体である化合物を製造することができる。 The present invention further provides a method for producing a silicone compound represented by the above formula (1). The production method comprises a compound represented by the following formula (8):
Figure 0006195419
 (In formula (8), Y is a monovalent group having a radical polymerizable group, and Z is a group that reacts with an amine or a halogen atom)
Compound represented by the following formula (9)
Figure 0006195419
 (Wherein A and B are as described above)
And a step of reacting. A compound that is liquid at room temperature can be produced through the above steps.

上記式（８）において、Ｙはラジカル重合性基を有する一価の基である。ラジカル重合性基としては、(メタ)アクリル基、スチリル基、インデニル基、アルケニル基、シクロアルケニル基、ノルボニル基、及び共役又は非共役アルカジエン基等が挙げられる。該Ｙは、例えば、下記（３’）または（４’）で示される基が好ましい。

Figure 0006195419
上記式（３’）及び（４’）において、Ｒ１は水素原子またはメチル基である。好ましくは反応性の観点からＲ１は水素原子であるのがよい。 In the above formula (8), Y is a monovalent group having a radical polymerizable group. Examples of the radical polymerizable group include (meth) acryl group, styryl group, indenyl group, alkenyl group, cycloalkenyl group, norbornyl group, and conjugated or non-conjugated alkadiene group. Y is preferably a group represented by the following (3 ′) or (4 ′), for example.
Figure 0006195419
 In the above formulas (3 ′) and (4 ′), R 1 is a hydrogen atom or a methyl group. Preferably, R 1 is a hydrogen atom from the viewpoint of reactivity.

上記式（８）において、Ｚはアミンと反応する基またはハロゲン原子である。例えば、ハロゲン化アルキル基、酸無水物基、エステル基、及びイソシアネート基等が挙げられる。ハロゲン原子としては、塩素、臭素、ヨウ素が挙げられる。中でも、反応性ならびに合成の容易さから、塩素原子またはイソシアネート基が好ましい。   In the above formula (8), Z is a group that reacts with an amine or a halogen atom. Examples thereof include a halogenated alkyl group, an acid anhydride group, an ester group, and an isocyanate group. Examples of the halogen atom include chlorine, bromine and iodine. Among these, a chlorine atom or an isocyanate group is preferable from the viewpoint of reactivity and ease of synthesis.

上記式（８）で表される化合物としては、（メタ）アクリル酸クロライド、及び（メタ）アクリル酸エチルイソシアネートが挙げられる。特に反応性（ラジカル重合性）の観点から、アクリル酸クロライドまたはアクリル酸エチルイソシアネートが好ましい。   Examples of the compound represented by the formula (8) include (meth) acrylic acid chloride and (meth) acrylic acid ethyl isocyanate. In particular, from the viewpoint of reactivity (radical polymerization), acrylic acid chloride or ethyl acrylate isocyanate is preferable.

例えば、下記式（５）で表される化合物は（メタ）アクリル酸クロライドを使用して製造できる。

Figure 0006195419
（式中、Ｒ１、Ｒ２、Ｒ４、ｎ、ｍ、及びｅは上記の通りである。） For example, the compound represented by the following formula (5) can be produced using (meth) acrylic acid chloride.
Figure 0006195419
 (In the formula, R 1 , R 2 , R 4 , n, m, and e are as described above.)

詳細には、上記式（５）で表される化合物は、下記式（１０）：

Figure 0006195419
（式中、Ｒ１は水素原子またはメチル基である）
で表される（メタ）アクリル酸クロライドと、下記式（１１）：
Figure 0006195419
 （式中、Ｒ２、Ｒ４、ｎ、ｍ、及びｅは上記の通りである）
で表される化合物を反応させて製造できる。 Specifically, the compound represented by the above formula (5) is represented by the following formula (10):
Figure 0006195419
 (Wherein R 1 is a hydrogen atom or a methyl group)
(Meth) acrylic acid chloride represented by the following formula (11):
Figure 0006195419
 (Wherein R 2 , R 4 , n, m, and e are as described above)
It can manufacture by making the compound represented by these react.

また、下記式（６）で表される化合物は、（メタ）アクリル酸エチルイソシアネートを使用して製造できる。

Figure 0006195419
（式中、Ｒ１、Ｒ２、Ｒ４、ｎ、ｍ、及びｅは上記の通りである） Moreover, the compound represented by following formula (6) can be manufactured using (meth) acrylic-acid ethyl isocyanate.
Figure 0006195419
 (Wherein R 1 , R 2 , R 4 , n, m, and e are as described above)

詳細には、上記式（６）で表される化合物は、下記式（１２）：

Figure 0006195419
（式中、Ｒ１は上記の通りである）
で表される化合物と、下記式（１３）：
Figure 0006195419
 （式中、Ｒ２、Ｒ４、ｎ、ｍ、及びｅは上記の通りである）
で表される化合物を反応させて製造できる。 Specifically, the compound represented by the above formula (6) is represented by the following formula (12):
Figure 0006195419
 (Wherein R 1 is as described above)
And a compound represented by the following formula (13):
Figure 0006195419
 (Wherein R 2 , R 4 , n, m, and e are as described above)
It can manufacture by making the compound represented by these react.

上記製造方法において、式（８）で表される化合物（上記式（１０）及び（１２）を包含する）の配合量は適宜選択すればよい。好ましくは、上記式（９）で表される化合物（上記式（１１）及び（１３）を包含する）１モル当たり、式（８）で表される化合物１〜３モルであり、更に好ましくは１．０５〜２モルであるのがよい。上記下限値より少ないと、式（９）で表される化合物の未反応物が生成物中に多く残存し、目的物の純度が低下する。また、上記上限値より多いとコスト高になるおそれがある。   In the said manufacturing method, what is necessary is just to select suitably the compounding quantity of the compound (including said Formula (10) and (12)) represented by Formula (8). Preferably, it is 1 to 3 moles of the compound represented by the formula (8) per mole of the compound represented by the above formula (9) (including the above formulas (11) and (13)), more preferably It is good that it is 1.05-2 mol. When less than the said lower limit, many unreacted substances of the compound represented by Formula (9) remain in a product, and the purity of a target object will fall. Further, if the amount is larger than the above upper limit value, the cost may increase.

上記反応は、アルカリ金属塩およびアルカリ土類金属塩の水溶液を共存させて行うことが出来る。アルカリ金属塩およびアルカリ土類金属塩の水溶液共存下で反応を行うことにより、未反応のラジカル重合性基含有化合物やその副生成物を除去する事が容易となる。アルカリ金属塩およびアルカリ土類金属塩としては、例えば、水酸化リチウム、炭酸リチウム、炭酸水素リチウム、水酸化ナトリウム、炭酸ナトリウム、炭酸水素ナトリウム、水素化ホウ素ナトリウム、水素化カリウム、水酸化カリウム、炭酸カリウム、炭酸水素カリウム、リン酸水素二カリウム等のアルカリ金属塩、または水酸化マグネシウム、炭酸マグネシウム、水酸化カルシウム、炭酸カルシウム、水酸化ストロンチウム、炭酸ストロンチウム、水酸化バリウム、炭酸バリウム等が挙げられる。中でも、入手容易性、取扱性、反応性および反応系中の化合物の安定性から、水酸化ナトリウム、炭酸ナトリウム、及び炭酸カリウムが好ましく、より好ましくは炭酸ナトリウムである。炭酸ナトリウムの添加量は、ラジカル重合性基を有する化合物１モルに対して１モル以上が好ましく、より好ましくは２モル以上である。   The above reaction can be carried out in the presence of an aqueous solution of an alkali metal salt and an alkaline earth metal salt. By performing the reaction in the presence of an aqueous solution of an alkali metal salt and an alkaline earth metal salt, it becomes easy to remove the unreacted radical polymerizable group-containing compound and its by-products. Examples of the alkali metal salt and alkaline earth metal salt include lithium hydroxide, lithium carbonate, lithium hydrogen carbonate, sodium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium borohydride, potassium hydride, potassium hydroxide, carbonate Examples thereof include alkali metal salts such as potassium, potassium hydrogen carbonate and dipotassium hydrogen phosphate, or magnesium hydroxide, magnesium carbonate, calcium hydroxide, calcium carbonate, strontium hydroxide, strontium carbonate, barium hydroxide and barium carbonate. Of these, sodium hydroxide, sodium carbonate, and potassium carbonate are preferred, and sodium carbonate is more preferred from the standpoint of availability, handleability, reactivity, and stability of the compound in the reaction system. The amount of sodium carbonate added is preferably 1 mol or more, more preferably 2 mol or more, per 1 mol of the compound having a radical polymerizable group.

反応温度は特に限定されないが、−２０〜６０℃が好ましく、特には０〜２０℃が好ましい。温度が−２０℃以下であると反応するのに特殊な装置が必要になる。また温度が６０℃を超えるとラジカル重合性基が重合反応を起こすおそれがある。   Although reaction temperature is not specifically limited, -20-60 degreeC is preferable and 0-20 degreeC is especially preferable. A special apparatus is required to react when the temperature is -20 ° C or lower. Moreover, when temperature exceeds 60 degreeC, there exists a possibility that a radically polymerizable group may raise | generate a polymerization reaction.

上記反応には、ラジカル重合性基の重合反応を防ぐ為に、各種重合禁止剤を添加しても良い。添加する重合禁止剤は特に限定されないが、ハイドロキノン、ハイドロキノンモノメチルエーテル、４，４’−ブチリデンビス（６−ｔ−ブチル−ｍ−クレゾール）、２，２’−メチレンビス（４−メチル−６−ｔ−ブチルフェノール）、２，２’−メチレンビス（４−エチル−６−ｔ−ブチルフェノール）、２，６−ジ−ｔ−ブチル−ｐ−クレゾール、２，５−ジ−ｔ−アミル−ハイドロキノン、２，５−ジ−ｔ−ブチル−ハイドロキノンなどが挙げられる。   Various polymerization inhibitors may be added to the above reaction in order to prevent the polymerization reaction of the radical polymerizable group. The polymerization inhibitor to be added is not particularly limited, but hydroquinone, hydroquinone monomethyl ether, 4,4′-butylidenebis (6-t-butyl-m-cresol), 2,2′-methylenebis (4-methyl-6-t-). Butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 2,6-di-t-butyl-p-cresol, 2,5-di-t-amyl-hydroquinone, 2,5 -Di-t-butyl-hydroquinone etc. are mentioned.

また、本発明のシリコーン化合物は、下記式で表すようなラジカル重合性基を導入したアルコキシシラン化合物を先に合成し、

Figure 0006195419
（上記各式において、Ｒ１、Ｒ４、ｎ、及びｅは上記の通りであり、Ｒは炭素数１〜３のアルキル基である）
該アルコキシシラン化合物と、ハロシリル基又はアルコキシシリル基を有するシリコーン化合物またはシラン化合物とを反応させることにより製造することもできる。しかし該製造方法では、先に導入したラジカル重合性基が反応中または精製段階での加熱により反応して着色または増粘を生じ、あるいはゲル化するおそれがある。この問題は特にラジカル重合性基がアクリル基である場合に顕著におこる。これはアクリル基の反応性が高い為である。従って、室温で液体の化合物を得るためには上述したようにラジカル重合性基を最後に導入するのが好ましい。 In addition, the silicone compound of the present invention first synthesizes an alkoxysilane compound into which a radical polymerizable group represented by the following formula is introduced,
Figure 0006195419
 (In the above formulas, R 1 , R 4 , n, and e are as described above, and R is an alkyl group having 1 to 3 carbon atoms)
It can also be produced by reacting the alkoxysilane compound with a silicone compound or silane compound having a halosilyl group or an alkoxysilyl group. However, in the production method, the radically polymerizable group introduced earlier may react with heating during the reaction or in the purification stage to cause coloring or thickening or gelation. This problem occurs particularly when the radical polymerizable group is an acrylic group. This is because the reactivity of the acrylic group is high. Therefore, in order to obtain a compound that is liquid at room temperature, it is preferable to introduce the radical polymerizable group last as described above.

上記の通り本発明のシリコーン化合物は融点が低く室温で液体であることができる。そのためハンドリング性に優れている。また、本発明のシリコーン化合物は良好な酸素透過性を有する硬化物を与える。さらに他のモノマー成分との相溶性に優れ、良好な反応性を有する。特に本発明のシリコーン化合物において、ラジカル重合性基（Ｘ）がアクリル基である化合物はメタクリル基である化合物に比較して硬化性が良好であるため、より好ましい。   As described above, the silicone compound of the present invention has a low melting point and can be liquid at room temperature. Therefore, it is excellent in handling properties. Moreover, the silicone compound of the present invention gives a cured product having good oxygen permeability. Furthermore, it is excellent in compatibility with other monomer components and has good reactivity. In particular, in the silicone compound of the present invention, a compound in which the radical polymerizable group (X) is an acryl group is more preferable because it has better curability than a compound in which the methacryl group is used.

本発明のシリコーン化合物と重合する他のモノマー化合物は特に限定されず、後述する用途に応じて、従来公知のものを使用することができる。例えば、Ｎ−ビニルピロリドン、Ｎ，Ｎ−ジメチルアクリルアミド、及びＮ−メチル−３−メチリデンピロリドンなどの窒素原子含有モノマー、メタクリル酸、及びヒドロキシエチル（メタ）アクリレート等の親水性モノマーが挙げられる。   Other monomer compounds that are polymerized with the silicone compound of the present invention are not particularly limited, and conventionally known monomer compounds can be used according to the use described later. Examples thereof include nitrogen atom-containing monomers such as N-vinylpyrrolidone, N, N-dimethylacrylamide, and N-methyl-3-methylidenepyrrolidone, and hydrophilic monomers such as methacrylic acid and hydroxyethyl (meth) acrylate.

本発明のシリコーン化合物を他のモノマー化合物に相溶させて得た組成物は、例えば眼用デバイス組成物、塗料、又は化粧料組成物として好適に使用することができる。化粧料組成物としては、例えば、スキンケア用、毛髪用、制汗剤用、脱臭剤用、メイクアップ用、又は紫外線防御用化粧料が挙げられる。   A composition obtained by compatibilizing the silicone compound of the present invention with another monomer compound can be suitably used as, for example, an ophthalmic device composition, a paint, or a cosmetic composition. Examples of the cosmetic composition include skin care, hair, antiperspirant, deodorant, makeup, and UV protection cosmetics.

以下、実施例及び比較例を示し、本発明をより詳細に説明するが、本発明は下記の実施例に制限されるものではない。   EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated in detail, this invention is not restrict | limited to the following Example.

以下の実施例において、分子構造は核磁気共鳴分光法（１Ｈ−ＮＭＲ）を用いた測定により決定した。実施例で用いた測定装置を以下に示す。
１Ｈ−ＮＭＲ：ＡＶＡＮＣＥ ＩＩＩ（ブルカー・バイオスピン株式会社） In the following examples, the molecular structure was determined by measurement using nuclear magnetic resonance spectroscopy ( 1 H-NMR). The measuring apparatus used in the examples is shown below.
1 H-NMR: AVANCE III (Bruker BioSpin Corporation)

［実施例１］
温度計、滴下ロート、窒素導入管を装着したフラスコに、下記式（Ｉ）のシリコーン含有アミン０．１ｍｏｌ、ヘキサン２００ｍｌならびに１０％炭酸ナトリウム水１７０ｇを加え、攪拌しながら、５℃下にてアクリル酸クロライド１．２ｍｏｌを滴下した。

Figure 0006195419
滴下後、室温にて５時間攪拌を継続した後、有機層を純水で洗浄した。続いて、洗浄後の溶液に、ｐ−メトキシフェノール（重合禁止剤）０．００８ｇを添加し、減圧下（６０℃、５ｔｏｒｒ）にて揮発成分を留去し、室温（２５℃）で淡黄色透明液状の生成物を得た。１Ｈ−ＮＭＲ測定により同定したところ、下記式（ＩＩ）で示される化合物であった。収率は９６．９％であった。
Figure 0006195419
 １Ｈ−ＮＭＲのスペクトルを以下に示す。
１Ｈ−ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３）：δ ０．０６（ｓ，５４Ｈ）、０．３３〜０．５０（ｍ，４Ｈ）、１．４９〜1.６７（ｍ，４Ｈ）、３．１８〜３．３８（ｍ，４Ｈ）、５．６１（ｄｄ，１Ｈ）、６．３２（ｄｄｄ，１Ｈ）、６．５５（ｄｄ，１Ｈ） [Example 1]
To a flask equipped with a thermometer, a dropping funnel and a nitrogen introduction tube, 0.1 mol of a silicone-containing amine of the following formula (I), 200 ml of hexane and 170 g of 10% aqueous sodium carbonate are added, and acrylic is stirred at 5 ° C. with stirring. 1.2 mol of acid chloride was added dropwise.
Figure 0006195419
 After dropping, stirring was continued at room temperature for 5 hours, and then the organic layer was washed with pure water. Subsequently, 0.008 g of p-methoxyphenol (polymerization inhibitor) is added to the washed solution, and volatile components are distilled off under reduced pressure (60 ° C., 5 torr), and light yellow at room temperature (25 ° C.). A clear liquid product was obtained. When identified by 1 H-NMR measurement, it was a compound represented by the following formula (II). The yield was 96.9%.
Figure 0006195419
 The spectrum of 1 H-NMR is shown below.
1 H-NMR (400 MHz, CDCl 3 ): δ 0.06 (s, 54H), 0.33 to 0.50 (m, 4H), 1.49 to 1.67 (m, 4H), 3.18 ˜3.38 (m, 4H), 5.61 (dd, 1H), 6.32 (ddd, 1H), 6.55 (dd, 1H)

［実施例２］
上記式（Ｉ）で表される化合物の代わりに下記式（ＩＩＩ）で表される化合物を使用した以外は実施例１の方法を繰返し、室温（２５℃）で淡黄色透明液状の生成物を得た。

Figure 0006195419
１Ｈ−ＮＭＲ測定により同定したところ、下記式（ＩＶ）で示されるシリコーン化合物であった。収率は９７．３％であった。
Figure 0006195419
 １Ｈ−ＮＭＲのスペクトルを以下に示す。
１Ｈ−ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３）：δ ０．００（ｓ，６Ｈ）、０．０７（ｓ，３６Ｈ）、０．３４〜０．４８（ｍ，４Ｈ）、１．４９〜1.６７（ｍ，４Ｈ）、３．１８〜３．３９（ｍ，４Ｈ）、５．６２（ｄｄ，１Ｈ）、６．３２（ｄｄｄ，１Ｈ）、６．５３（ｄｄ，１Ｈ） [Example 2]
The method of Example 1 was repeated except that the compound represented by the following formula (III) was used in place of the compound represented by the above formula (I) to produce a pale yellow transparent liquid product at room temperature (25 ° C.). Obtained.
Figure 0006195419
 When identified by 1 H-NMR measurement, it was a silicone compound represented by the following formula (IV). The yield was 97.3%.
Figure 0006195419
 The spectrum of 1 H-NMR is shown below.
1 H-NMR (400 MHz, CDCl 3 ): δ 0.00 (s, 6H), 0.07 (s, 36H), 0.34 to 0.48 (m, 4H), 1.49 to 1.67 (M, 4H), 3.18-3.39 (m, 4H), 5.62 (dd, 1H), 6.32 (ddd, 1H), 6.53 (dd, 1H)

［実施例３］
アクリル酸クロライドの代わりに２−アクリロイルオキシエチルイソシアネートを使用した以外は実施例１の方法を繰返し、室温（２５℃）で淡黄色透明液状の生成物を得た。１Ｈ−ＮＭＲ測定により同定したところ、下記式（Ｖ）で示されるシリコーン化合物であった。収率は９５．２％であった。

Figure 0006195419
１Ｈ−ＮＭＲのスペクトルを以下に示す。
１Ｈ−ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３）：δ ０．０７（ｓ，５４Ｈ）、０．３４〜０．４５（ｍ，４Ｈ）、１．４９〜1.６８（ｍ，４Ｈ）、３．０８〜３．２０（ｍ，４Ｈ）、３．４９〜３．５９（ｍ，２Ｈ）、４．１８〜４．２８（ｍ，２Ｈ）、４．７２（ｂｒ，１Ｈ）、５．８２（ｄｄ，１Ｈ）、６．１５（ｄｄｄ，１Ｈ）、６．３９（ｄｄ，１Ｈ） [Example 3]
The method of Example 1 was repeated except that 2-acryloyloxyethyl isocyanate was used in place of acrylic acid chloride to obtain a light yellow transparent liquid product at room temperature (25 ° C.). When identified by 1 H-NMR measurement, it was a silicone compound represented by the following formula (V). The yield was 95.2%.
Figure 0006195419
 The spectrum of 1 H-NMR is shown below.
1 H-NMR (400 MHz, CDCl 3 ): δ 0.07 (s, 54H), 0.34 to 0.45 (m, 4H), 1.49 to 1.68 (m, 4H), 3.08 To 3.20 (m, 4H), 3.49 to 3.59 (m, 2H), 4.18 to 4.28 (m, 2H), 4.72 (br, 1H), 5.82 (dd , 1H), 6.15 (ddd, 1H), 6.39 (dd, 1H)

［実施例４］
アクリル酸クロライドの代わりに２−メタクリロイルオキシエチルイソシアネートを使用した以外は実施例１の方法を繰返し、室温（２５℃）で淡黄色透明液状の生成物を得た。１Ｈ−ＮＭＲ測定により同定したところ、下記式（ＶＩ）で示されるシリコーン化合物であった。収率は９６．５％であった。

Figure 0006195419
１Ｈ−ＮＭＲのスペクトルを以下に示す。
１Ｈ−ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３）：δ ０．０７（ｓ，５４Ｈ）、０．３４〜０．４２（ｍ，４Ｈ）、１．４９〜1.６９（ｍ，４Ｈ）、１．９３（ｍ，３Ｈ）、３．０６〜３．１８（ｍ，４Ｈ）、３．４８〜３．５８（ｍ，２Ｈ）、４．１９〜４．３０（ｍ，２Ｈ）、４．７４（ｂｒ，１Ｈ）、５．５５（ｓ，１Ｈ）、６．０９（ｓ，１Ｈ） [Example 4]
The method of Example 1 was repeated except that 2-methacryloyloxyethyl isocyanate was used instead of acrylic acid chloride to obtain a light yellow transparent liquid product at room temperature (25 ° C.). When identified by 1 H-NMR measurement, it was a silicone compound represented by the following formula (VI). The yield was 96.5%.
Figure 0006195419
 The spectrum of 1 H-NMR is shown below.
1 H-NMR (400 MHz, CDCl 3 ): δ 0.07 (s, 54H), 0.34 to 0.42 (m, 4H), 1.49 to 1.69 (m, 4H), 1.93 (M, 3H), 3.06 to 3.18 (m, 4H), 3.48 to 3.58 (m, 2H), 4.19 to 4.30 (m, 2H), 4.74 (br , 1H), 5.55 (s, 1H), 6.09 (s, 1H)

［実施例５］
アクリル酸クロライドの代わりにメタクリル酸クロライドを使用した以外は実施例２の方法を繰返し、室温（２５℃）で淡黄色透明液状の生成物を得た。１Ｈ−ＮＭＲ測定により同定したところ、下記式（ＶＩＩ）で示されるシリコーン化合物であった。収率は９７．４％であった。

Figure 0006195419
１Ｈ−ＮＭＲのスペクトルを以下に示す。
１Ｈ−ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３）：δ ０．００（ｓ，６Ｈ）、０．０７（ｓ，３６Ｈ）、０．３４〜０．４８（ｍ，４Ｈ）、１．４９〜1.６７（ｍ，４Ｈ）、１．９６（ｍ，３Ｈ）、３．１６〜３．３７（ｍ，４Ｈ）、５．０５（ｓ，１Ｈ）、５．２０（ｓ，１Ｈ） [Example 5]
The method of Example 2 was repeated except that methacrylic acid chloride was used instead of acrylic acid chloride to obtain a light yellow transparent liquid product at room temperature (25 ° C.). When identified by 1 H-NMR measurement, it was a silicone compound represented by the following formula (VII). The yield was 97.4%.
Figure 0006195419
 The spectrum of 1 H-NMR is shown below.
1 H-NMR (400 MHz, CDCl 3 ): δ 0.00 (s, 6H), 0.07 (s, 36H), 0.34 to 0.48 (m, 4H), 1.49 to 1.67 (M, 4H), 1.96 (m, 3H), 3.16-3.37 (m, 4H), 5.05 (s, 1H), 5.20 (s, 1H)

［参考例１］
温度計、滴下ロート、窒素導入管を装着したフラスコに、下記式（ＩＸ）：

Figure 0006195419
で表されるアミン基含有アルコキシシラン０．１ｍｏｌ、トルエン２００ｍｌ、及びトリエチルアミン０．１２ｍｏｌを加え、攪拌しながら５℃下にてアクリル酸クロライド０．１１ｍｏｌを滴下した。滴下後、室温にて５時間攪拌を継続した後、メタノール０．３ｍｏｌを加えて更に３０分間攪拌をした。続いて、有機層を純水で洗浄し、洗浄後の溶液にｐ−メトキシフェノール（重合禁止剤）０．００８ｇを添加し、減圧下（６０℃、５ｔｏｒｒ）にて揮発成分を留去する事で黄色液体状の生成物を得た。１Ｈ−ＮＭＲ測定により同定したところ、下記式（Ｘ）で表される化合物であった。収率は９２．９％であった。
Figure 0006195419
 続いて、温度計、滴下ロート、窒素導入管を装着したフラスコに、水２０ｍｌ、メタノール２０ｍｌ、及びヘキサン４０ｍｌを添加し、５℃下にて、上記化合物（Ｘ）０．０３ｍｏｌ及びトリメチルクロロシラン０．２７ｍｏｌの混合物を滴下した。滴下終了後、室温にて３時間撹拌してから、有機層を純水で洗浄し、洗浄後の溶液にｐ−メトキシフェノール（重合禁止剤）０．００３ｇを添加した。減圧下（６０℃、５ｔｏｒｒ）にて揮発成分を留去している間に、得られた反応液はゲル化した。 [Reference Example 1]
In a flask equipped with a thermometer, a dropping funnel and a nitrogen introduction tube, the following formula (IX):
Figure 0006195419
 0.1 mol of amine group-containing alkoxysilane represented by the formula, 200 ml of toluene and 0.12 mol of triethylamine were added, and 0.11 mol of acrylic acid chloride was added dropwise at 5 ° C. with stirring. After the dropwise addition, stirring was continued at room temperature for 5 hours, 0.3 mol of methanol was added, and stirring was continued for 30 minutes. Subsequently, the organic layer is washed with pure water, 0.008 g of p-methoxyphenol (polymerization inhibitor) is added to the washed solution, and volatile components are distilled off under reduced pressure (60 ° C., 5 torr). Yielded a yellow liquid product. When identified by 1 H-NMR measurement, it was a compound represented by the following formula (X). The yield was 92.9%.
Figure 0006195419
 Subsequently, 20 ml of water, 20 ml of methanol, and 40 ml of hexane were added to a flask equipped with a thermometer, a dropping funnel, and a nitrogen introduction tube, and 0.03 mol of the above compound (X) and trimethylchlorosilane, 0. 27 mol of the mixture was added dropwise. After completion of the dropping, the mixture was stirred at room temperature for 3 hours, and then the organic layer was washed with pure water, and 0.003 g of p-methoxyphenol (polymerization inhibitor) was added to the washed solution. While the volatile component was distilled off under reduced pressure (60 ° C., 5 torr), the resulting reaction solution gelled.

［参考例２］
上記参考例１においてアクリル酸クロライドの代わりに２−アクリロイルオキシエチルイソシアネートを使用した以外は参考例１の方法を繰返した。参考例１と同じく、得られた反応液は精製の間にゲル化した。 [Reference Example 2]
The method of Reference Example 1 was repeated except that 2-acryloyloxyethyl isocyanate was used instead of acrylic acid chloride in Reference Example 1. As in Reference Example 1, the resulting reaction solution gelled during purification.

［比較例１］
３−［トリス（トリメチルシロキシ）シリル］プロピルアクリルアミド（ＴＲＩＳ−Ａ）の合成
上記式（Ｉ）で表される化合物の代わりに［（ＣＨ３）３ＳｉＯ］３Ｓｉ（ＣＨ２）３−ＮＨ２を使用した以外は実施例１の方法を繰返し、室温（２５℃）で白色固体状の生成物を得た。１Ｈ−ＮＭＲ測定により同定したところ、下記式（ＶＩＩＩ）で示されるシリコーン化合物であった。収率は９３．１％であった。

Figure 0006195419
１Ｈ−ＮＭＲのスペクトルを以下に示す。
１Ｈ−ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３）：δ ０．０９（ｓ，２７Ｈ）、０．４５〜０．５０（ｍ，２Ｈ）、１．５９（ｍ，２Ｈ）、３．３２（ｍ，２Ｈ）、５．５８（ｂｒ，１Ｈ）、５．６２（ｄｄ，１Ｈ）、６．０６（ｄｄｄ，１Ｈ）、６．２５（ｄｄ，１Ｈ） [Comparative Example 1]
Synthesis of 3- [tris (trimethylsiloxy) silyl] propylacrylamide (TRIS-A) [(CH 3 ) 3 SiO] 3 Si (CH 2 ) 3 —NH 2 instead of the compound represented by the above formula (I) The method of Example 1 was repeated except that was used to obtain a white solid product at room temperature (25 ° C.). When identified by 1 H-NMR measurement, it was a silicone compound represented by the following formula (VIII). The yield was 93.1%.
Figure 0006195419
 The spectrum of 1 H-NMR is shown below.
1 H-NMR (400 MHz, CDCl 3 ): δ 0.09 (s, 27H), 0.45 to 0.50 (m, 2H), 1.59 (m, 2H), 3.32 (m, 2H) ), 5.58 (br, 1H), 5.62 (dd, 1H), 6.06 (ddd, 1H), 6.25 (dd, 1H)

実施例１〜５及び比較例１で得たシリコーン化合物の室温（２５℃）での状態を下記表１にまとめた。   The states at room temperature (25 ° C.) of the silicone compounds obtained in Examples 1 to 5 and Comparative Example 1 are summarized in Table 1 below.

Figure 0006195419
Figure 0006195419

比較例１で得た化合物（３−［トリス（トリメチルシロキシ）シリル］プロピルアクリルアミド（ＴＲＩＳ−Ａ））は融点が５１℃であり室温（２５℃）で固体であった。これに対し、本発明のシリコーン化合物は、室温（２５℃）で液体であり取り扱い性が良好であった。   The compound (3- [tris (trimethylsiloxy) silyl] propylacrylamide (TRIS-A)) obtained in Comparative Example 1 had a melting point of 51 ° C. and was solid at room temperature (25 ° C.). On the other hand, the silicone compound of the present invention was liquid at room temperature (25 ° C.) and was easy to handle.

［比較例２］
上記式（Ｉ）で表される化合物の代わりに［（ＣＨ３）３ＳｉＯ］３Ｓｉ（ＣＨ２）３−ＮＨ−Ｃ６Ｈ１３を使用した以外は実施例１の方法を繰返し、室温（２５℃）で淡黄色液体の生成物を得た。１Ｈ−ＮＭＲ測定により同定したところ、下記式（ＸＩ）で示されるシリコーン化合物であった。収率は９１．０％であった。

Figure 0006195419
１Ｈ−ＮＭＲのスペクトルを以下に示す。
１Ｈ−ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３）：δ ０．０９（ｓ，２７Ｈ）、０．３５−０．４６（ｍ，２Ｈ）、０．８５−０．９３（ｍ，３Ｈ）、１．２３−１．３６（ｍ，６Ｈ）、１．１２−１．５２（ｍ，４Ｈ）、３．２１−３．３３（ｍ，２Ｈ）、３．３３−３．４０（ｍ，２Ｈ）、５．６３（ｄｄ，１Ｈ）、６．３４（ｄｄｄ，１Ｈ）、６．５４（ｄｄ，１Ｈ） [Comparative Example 2]
The method of Example 1 was repeated except that [(CH 3 ) 3 SiO] 3 Si (CH 2 ) 3 —NH—C 6 H 13 was used instead of the compound represented by the above formula (I), and room temperature ( 25 ° C), a pale yellow liquid product was obtained. When identified by 1 H-NMR measurement, it was a silicone compound represented by the following formula (XI). The yield was 91.0%.
Figure 0006195419
 The spectrum of 1 H-NMR is shown below.
1 H-NMR (400 MHz, CDCl 3 ): δ 0.09 (s, 27H), 0.35-0.46 (m, 2H), 0.85-0.93 (m, 3H), 1.23 -1.36 (m, 6H), 1.12-1.52 (m, 4H), 3.21-3.33 (m, 2H), 3.33-3.40 (m, 2H), 5 .63 (dd, 1H), 6.34 (ddd, 1H), 6.54 (dd, 1H)

［硬化物の製造］
反応容器に、実施例及び比較例で得た各化合物（６５質量部）、Ｎ，Ｎ−ジメチルアクリルアミド（３４質量部）、トリエチレングリコールジメタクリレート（１質量部）、ダロキュア１１７３（チバ・スペシャリティー・ケミカルズ社製、０．５質量部）を入れ、混合撹拌した。得られた混合物を脱気した後、エチレン-ビニルアルコール樹脂製の金型に注入し、窒素雰囲気下でメタルハライドランプを用いて硬化を行った。各化合物を含む混合物について、硬化に要したエネルギーを表２に記載する。 [Manufacture of cured products]
In a reaction vessel, each compound (65 parts by mass) obtained in Examples and Comparative Examples, N, N-dimethylacrylamide (34 parts by mass), triethylene glycol dimethacrylate (1 part by mass), Darocur 1173 (Ciba Specialty) -The chemicals company make, 0.5 mass part) was put, and it mixed and stirred. The resulting mixture was degassed and then poured into a mold made of ethylene-vinyl alcohol resin and cured using a metal halide lamp in a nitrogen atmosphere. The energy required for curing is shown in Table 2 for the mixture containing each compound.

上記で得られた各硬化物をイソプロピルアルコールに１０時間浸漬した。その後、水／イソプロピルアルコール＝１：１の溶液に１０時間、更に純水に２０時間浸漬した。浸漬後の各硬化物について、酸素透過率をフィルム酸素透過率計Ｋ−３１６（ツクバリカセイキ株式会社製）を用いて測定した。結果を表２に記載する。   Each cured product obtained above was immersed in isopropyl alcohol for 10 hours. Then, it was immersed in a solution of water / isopropyl alcohol = 1: 1 for 10 hours and further in pure water for 20 hours. About each hardened | cured material after immersion, the oxygen permeability was measured using the film oxygen permeability meter K-316 (made by Tsukubarika Seiki Co., Ltd.). The results are listed in Table 2.

Figure 0006195419
Figure 0006195419

本発明のシリコーン化合物は、比較例１のシリコーン化合物（Ｔｒｉｓ−Ａ）及び比較例２のシリコーン化合物に比較して、高い酸素透過性を有する硬化物を与えることができる。また他のモノマー成分との相溶性に優れ、反応性も良好である。   Compared with the silicone compound of Comparative Example 1 (Tris-A) and the silicone compound of Comparative Example 2, the silicone compound of the present invention can give a cured product having high oxygen permeability. Moreover, it is excellent in compatibility with other monomer components and has good reactivity.

本発明のシリコーン化合物は酸素透過性の高い硬化物を与えることができる。また融点が低く室温で液体であることができるため、取り扱い性が良好である。さらに反応性も良好である。本発明のシリコーン化合物は、眼用デバイス組成物、塗料、及び、スキンケア、毛髪、制汗剤、脱臭剤、メイクアップ、又は紫外線防御用の化粧料組成物等に有用である。   The silicone compound of the present invention can give a cured product having high oxygen permeability. In addition, since the melting point is low and it can be liquid at room temperature, it is easy to handle. Furthermore, the reactivity is also good. The silicone compound of the present invention is useful for ophthalmic device compositions, paints, and cosmetic compositions for skin care, hair, antiperspirants, deodorants, makeup, or UV protection.

Claims (5)

下記式（６）で表されるシリコーン化合物
Figure 0006195419
 （式中、Ｒ １ は水素原子またはメチル基であり、Ｒ ２ 及びＲ ４ は互いに独立に、炭素数１〜１０のアルキル基であり、ｎは１〜６の整数であり、ｍは１〜６の整数であり、ｅは互いに独立に１、２、又は３である）。 Silicone compound represented by the following formula ( 6 )
Figure 0006195419
 Wherein R 1 is a hydrogen atom or a methyl group, R 2 and R 4 are each independently an alkyl group having 1 to 10 carbon atoms, n is an integer of 1 to 6, and m is 1 to 6 is an integer of 6 and e is 1, 2, or 3 independently of each other) . ｎ及びｍが３である、請求項１記載のシリコーン化合物。 n and m are 3, claim 1 silicone compound according. Ｒ１が水素原子である、請求項１又は２記載のシリコーン化合物。 The silicone compound according to claim 1 or 2 , wherein R 1 is a hydrogen atom. 下記式（６）で表されるシリコーン化合物の製造方法であって、
Figure 0006195419
 （式中、Ｒ １ は水素原子またはメチル基であり、Ｒ ２ 及びＲ ４ は互いに独立に、炭素数１〜１０のアルキル基であり、ｎは１〜６の整数であり、ｍは１〜６の整数であり、ｅは互いに独立に１、２、又は３である）
下記式（１２）で表される化合物：
Figure 0006195419
 （式中、Ｒ １ は水素原子またはメチル基である）と
下記式（１３）で表される化合物：
Figure 0006195419
 （式中、Ｒ ２ 及びＲ ４ は互いに独立に、炭素数１〜１０のアルキル基であり、ｎは１〜６の整数であり、ｍは１〜６の整数であり、ｅは互いに独立に１、２、又は３である）
とを反応させて、上記式（６）で表されるシリコーン化合物を得る工程を含む、前記製造方法。 A method for producing a silicone compound represented by the following formula ( 6 ):
Figure 0006195419
 Wherein R 1 is a hydrogen atom or a methyl group, R 2 and R 4 are each independently an alkyl group having 1 to 10 carbon atoms, n is an integer of 1 to 6, and m is 1 to 6 is an integer, and e is 1, 2, or 3 independently of each other)
Compound represented by the following formula (12):
Figure 0006195419
 (Wherein R 1 is a hydrogen atom or a methyl group) and
Compound represented by the following formula (13):
Figure 0006195419
 Wherein R 2 and R 4 are each independently an alkyl group having 1 to 10 carbon atoms, n is an integer of 1 to 6, m is an integer of 1 to 6, and e is independently of each other. 1, 2, or 3)
The said manufacturing method including the process of making these react and obtaining the silicone compound represented by the said Formula (6) . Ｒ１が水素原子である、請求項４記載の製造方法。 The production method according to claim 4 , wherein R 1 is a hydrogen atom.
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